GREEN DIESEL BLENDS DESIGN USING DECOMPOSITION-BASED...
Transcript of GREEN DIESEL BLENDS DESIGN USING DECOMPOSITION-BASED...
GREEN DIESEL BLENDS DESIGN USING DECOMPOSITION-BASED
OPTIMIZATION APPROACH
PHOON LI YEE
UNIVERSITI TEKNOLOGI MALAYSIA
GREEN DIESEL BLENDS DESIGN USING DECOMPOSITION-BASED
OPTIMIZATION APPROACH
PHOON LI YEE
A thesis submitted in fulfilment of the
requirements for the award of the degree of
Doctor of Philosophy (Chemical Engineering)
Faculty of Chemical and Energy Engineering
Universiti Teknologi Malaysia
APRIL 2017
iii
Specially dedicated to my parents, family and friends
Thanks for their support and encouragement along the journey
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ACKNOWLEDGEMENT
It has been a long journey toward the completion of this thesis, I would like
to express my heartfelt gratitude to those individuals who have guided me, support
and motivate me along the journey. This thesis would not complete successfully
without the support and guidance from my main supervisor Dr. Azizul Azri
Mustaffa, my co-supervisors Assoc. Prof. Dr. Haslenda Hashim and Assoc. Prof. Dr.
Ramli Mat. I would like to take this opportunity to thank for their endless supports,
valuable advices and suggestions over the past years, which have stimulated the ideas
for me to continue my research.
I also would like to express my heartiest appreciation to Professor Dr. Rafiqul
Gani, whom had provided a great help during my research attachment in Technical
University of Denmark (DTU). Next, special thanks to Assoc. Prof. Dr. Gholamreza
Zahedi and my dearest partner, Ze Wei who have got me to where I am today.
My deeply appreciation also won‟t leave to my family and my friends,
especially for those fellow post-graduate students in the Process Systems
Engineering Centre (PROSPECT) for their continuous spiritual support and
encouragement.
Last but not least, the tremendous financial support granted by Ministry of
Education Malaysia via MyPhD scholarship and the financial supports from GUP
grants of Universiti Teknologi Malaysia also should not been forgotten.
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ABSTRACT
Petrodiesel-biofuel/biochemical blend (green diesel blend) is a promising
solution in reducing environmental impact while improving the performance of
petrodiesel. A systematic computer-aided approach can efficiently solve green diesel
blends‟ design problems to replace the iterative, costly and time-consuming
experimental trial-and-error approach. Other than the engine performance related
fuel properties (density, kinematic viscosity, cetane number and higher heating
value), the safety indicator: flash point is an important safety consideration for diesel
fuel and it should be considered in the green diesel blend design to avoid fire
accident. The aims of this study are to develop a systematic computer-aided tailor-
made green diesel blend design algorithm and to improve the flash point prediction
model, which is the Liaw model for B5 palm oil biodiesel (B5)-ester/ether/alcohol
blends. The algorithm contains two main phases: the model-based design and the
experimental validation. The optimum green diesel blend is computationally
optimized in the model-based design phase. The accuracy of the Liaw model using
UNIFAC type models is improved for B5-ester/ether/alcohol by regressing the
UNIFAC group interaction parameters. The verified and improved Liaw models are
embedded into the model-based design phase to optimize the green diesel blend. The
physicochemical property, engine performance and emissions of the optimum blend
obtained in the model-based design phase are experimentally validated in the
experimental validation phase. The application of the developed design algorithm is
illustrated by finding the right combination of the binary and ternary blends of B5-
ester/ether/alcohol. The ideal Liaw model, the Liaw model using the original
UNIFAC and the Liaw model using original UNIFAC with parameters set B (group
interaction parameter between CH2 and OH are revised) are used to predict the flash
points of the B5-ether, B5-ester and B5-alcohol blends. GB3 (B5-11.1 % by mass of
diethyl succinate) and GT1 (B5-24.1% octanol-5.9 % diethyl succinate, by mass %)
with or without the cetane enhancer: 2-ethylhexyl nitrate (2EHN) are the optimum
binary and ternary blends with the high oxygen content obtained in the model-based
design phase. Satisfactory experimental validation results were obtained in
experimental validation phase and GT1A (GT1-0.17 % by mass of 2EHN) ) was
identified to be the most promising green diesel blend owning to its lower emissions
of nitrogen oxide (19.21 % lower than B5), un-burnt hydrocarbon (27.48 % lower
than B5) and carbon monoxide (36.73 % lower than B5). Meanwhile, GT1A has
comparative fuel efficiency to B5. The developed green diesel blend design
algorithm serves as an improved model for solving green diesel blend design
problem.
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ABSTRAK
Adunan petrodiesel-bahan api bio/biokimia (adunan diesel hijau) ialah
penyelesaian yang menjanjikan pengurangan impak terhadap alam sekitar serta
meningkatkan prestasi petrodiesel. Pendekatan berbantukan komputer yang
bersistematik dapat menyelesaikan secara cekap masalah reka bentuk adunan diesel
hijau untuk menggantikan kaedah cuba dan jaya secara eksperimen yang melibatkan
lelaran, mahal dan mengambil masa. Selain daripada prestasi enjin yang berkaitan
dengan sifat-sifat bahan api (ketumpatan, kelikatan kinematik, nombor setana dan
nilai pemanasan tinggi), penunjuk keselamatan: takat kilat ialah satu pertimbangan
keselamatan yang penting bagi bahan api diesel dan ia perlu dipertimbangkan di
dalam reka bentuk adunan diesel hijau untuk mengelakkan kemalangan kebakaran.
Kajian ini bertujuan untuk membangunkan satu algoritma reka bentuk adunan diesel
hijau buatan-sesuaian berbantukan komputer yang bersistematik dan memperbaiki
model ramalan takat kilat, iaitu model Liaw bagi adunan biodiesel minyak sawit B5
(B5)-ester/eter/alkohol. Algoritma tersebut mengandungi dua fasa utama: reka
bentuk berasaskan model dan pengesahan eksperimen. Adunan diesel optimum hijau
dikirakan secara berkomputer dalam fasa reka bentuk berasaskan model. Ketepatan
model Liaw yang menggunakan model jenis UNIFAC dipertingkatkan melalui
regresi parameter interaksi kumpulan UNIFAC bagi B5-ester/eter/alkohol. Model
Liaw yang telah disahkan dan diperbaiki kemudiannya dibenamkan ke dalam fasa
reka bentuk berasaskan model untuk mengoptimumkan adunan diesel hijau. Sifat
fizikokimia, prestasi dan pelepasan enjin bagi adunan optimum yang diperoleh pada
fasa reka bentuk berasaskan model disahkan secara eksperimen dalam fasa
pengesahan eksperimen. Penggunaan algoritma reka bentuk yang telah dibangunkan
ini ditunjukkan dengan mencari kombinasi yang betul bagi adunan perduaan dan
pertigaan B5-ester/eter/alkohol. Model Liaw unggul, model Liaw yang menggunakan
UNIFAC asal dan model Liaw yang menggunakan UNIFAC asal dengan parameter
set B (parameter interaksi antara kumpulan CH2 dan OH yang telah disemak semula)
digunakan untuk meramalkan takat kilat bagi adunan B5-eter, B5-ester dan B5-
alkohol. GB3 (B5-11.1 % jisim dietil suksinat) dan GT1 (B5-24.1 % jisim oktanol-
5.9 % jisim dietil suksinat) dengan atau tanpa penggalak setana: 2-etilheksil nitrat
(2EHN) ialah adunan perduaan and pertigaan optimum dengan kandungan oksigen
yang tinggi yang diperoleh di fasa reka bentuk berasaskan model. Keputusan
pengesahan eksperimen yang baik telah diperoleh pada fasa pengesahan eksperimen
dan GT1A (GT1-0.17% jisim 2EHN)) dikenalpasti sebagai adunan diesel hijau yang
terbaik kerana ia dapat mengurangkan pelepasan nitrogen oksida (19.21 % lebih
rendah daripada B5), hidrokarbon tidak terbakar (27.48 % lebih rendah daripada B5)
dan karbon monoksida (36.73 % lebih rendah daripada B5). Sementara itu, GT1A
mempunyai prestasi enjin yang setanding dengan B5. Algoritma reka bentuk adunan
diesel hijau yang telah dibangunkan menyediakan satu model diperbaiki untuk
menyelesaikan masalah reka bentuk adunan diesel hijau.
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TABLE OF CONTENTS
CHAPTER TITLE PAGE
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES xiii
LIST OF FIGURES xvi
LIST OF ABBREVIATION xix
LIST OF SYMBOLS xxii
LIST OF APPENDICES xxv
1 INTRODUCTION 1
1.1 Research Background 1
1.2 Problem Statement 6
1.3 Research Objectives 10
1.4 Research Scopes 11
1.5 Research Contribution 11
1.6 Thesis Outline 12
2 LITERATURE REVIEW 13
2.1 Petrodiesel 13
2.2 Biofuel as Petrodiesel Replacement 17
2.2.1 Biodiesel 20
2.2.2 Green Diesel or Renewable Diesel 21
2.2.3 Dimethyl Ether (DME) 22
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2.2.4 Fischer-Tropsch Renewable Diesel 24
2.2.5 Summary of Biofuel as Petrodiesel
Replacement
24
2.3 Tailor-Made Green Diesel Blends 28
2.3.1 Biodiesel-Petrodiesel Blends 31
2.3.2 Alcohol-Petrodiesel Blends (Diesohol) 33
2.3.3 Biodiesel-Alcohol-Petrodiesel Blends 34
2.3.4 Blends Containing Other Lignocellulosic
Bio-chemical
35
2.3.5 Summary of Tailor-Made Green Diesel
Blends
37
2.4 Significances and Specifications of Diesel Fuel‟s
Properties
38
2.5 Tailor-Made Green Diesel Blend Design 46
2.5.1 Computer-Aided Product Design Approach 47
2.6 Mixture Property Prediction Models 51
2.6.1 The Flash Point Prediction Models 52
2.6.1.1 Empirical Flash Point Prediction
Model based on Normal Boiling
Point and Composition Ranges
52
2.6.1.2 Flash Point Prediction Model based
on Molecular Structure:
Quantitative Structure-Property
Relationships (QSPR) Technique
52
2.6.1.3 Flash Point Prediction Model Based
on Vapor Pressure
54
2.6.1.4 Comparison of Flash Point
Prediction Models
58
2.7 Diesel Engine Performance and Emission 63
2.7.1 Engine Performance 63
2.7.2 Engine Emissions 68
2.7.3 Summary of Diesel Engine Performance
and Emission
70
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2.8 Cost Effectiveness and Reliability of Biofuel 70
3 METHODOLOGY 72
3.1 Introduction 72
3.2 Methodology Overview 73
3.2.1 Model-Based Design Phase 73
3.2.2 Experimental Validation Phase 75
3.2.3 Tools and Methods 76
3.3 The Main Ingredient and the Blending Agents of
Tailor-Made Green Diesel Blends
78
3.4 The Model-Based Design Phase 79
3.4.1 Stage 1: Problem Formulation 79
3.4.1.1 Task 1.1: Problem Definition 79
3.4.1.2 Task 1.2: Property Model
Identification
81
3.4.1.3 Summary of Stage 1 82
3.4.2 Stage 2: Decomposition-Based Computer-
aided Optimization
84
3.4.2.1 Task 2.1: Generation of Feasible
Blend Candidates
84
3.4.2.2 Task 2.2: Generation of Feasible
Blends
86
3.4.2.3 Task 2.3: Ranking and Select 90
3.4.3 Stage 3: Fuel Enhancement 91
3.4.3.1 Task 3.1: Identify the Fuel Qualities
to Enhance
91
3.4.3.2 Task 3.2: Find the Possible Fuel
Additives
92
3.4.3.3 Task 3.3: Verify the Compatibility 92
3.4.3.4 Task 3.4: Select the Final Additive 92
3.5 Improvement of the Flash Point Prediction
Model: Liaw Model for Tailor-Made Green
Diesel Blends
92
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3.5.1 Material and Experimental Methods for
Flash Point Determination
93
3.5.2 The Liaw Models for B5-
Ester/Ether/Alcohol Blends
94
3.5.2.1 The Effect of Different B5
Compositions to the Accuracy of
Liaw Model
95
3.5.2.2 The Antoine Equation used to
Estimate the Vapor Pressure
96
3.5.2.3 The UNIFAC-type Models used to
Estimate the Activity Coefficient
97
3.5.2.4 Evaluation of the Flash Point
Prediction
98
3.5.3 Improvement of Flash Point Prediction 98
3.6 The Experimental Validation Phase-Stage 4:
Experimental Validation
101
3.6.1 Blend Preparation 101
3.6.2 Task 4.1: Property Validation 102
3.6.3 Task 4.2: Fuel Performance and Emission
Test
103
3.6.3.1 Experimental Setup 103
3.6.3.2 Engine Performance Procedure 105
3.6.3.3 Equations and Evaluation 106
3.7 Summary 108
4 FLASH POINT PREDICTION OF TAILOR-
MADE GREEN DIESEL BLENDS
110
4.1 Introduction 110
4.2 Analysis of the Flash Point Prediction Accuracy
of the Liaw Models using UNIFAC-Type Models
110
4.2.1 Experimental Flash Point Results 110
4.2.2 Validation of B5 as Pseudo Homogenous
Mixture
112
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4.2.3 The Effect of Variant Petrodiesel
Compositions towards the Flash Point
Prediction
113
4.2.4 Flash Point Prediction using UNIFAC
Group Contribution Methods
114
4.3 Improvement of Flash Point Prediction for B5-
alcohol Blends
118
4.3.1 Revision of UNIFAC Group Interaction
Parameters
118
4.3.2 Flash Point Prediction using Revised Group
Interaction Parameters
119
4.3.3 Validation of Revised Group Interaction
Parameters for Flash Point Prediction
125
4.3.3.1 B5-Alcohol Blends (Test Set Data) 125
4.3.3.2 Ternary Blends of B5-EL-BU 127
4.4 Summary 130
5 OPTIMIZATION OF TAILOR-MADE GREEN
DIESEL BLENDS
132
5.1 Introduction 132
5.2 Stage 2: Decomposition-Based Computer-Aided
Optimization of Green Diesel Blends
133
5.2.1 Task 2.1: The Feasible Green Diesel Blend
Candidates
133
5.2.2 Task 2.2: The Feasible Green Diesel Blends 139
5.2.3 Task 2.3: The Best Optimum Green Diesel
Blends
143
5.2.4 Summary of Stage 2 147
5.3 Stage 3: Fuel Enhancement 148
5.3.1 Task 3.1: The Fuel Qualities to Enhance 148
5.3.2 Task 3.2: The Possible Fuel Additives 149
5.3.3 Task 3.3: The Compatibility of Green
Diesel Blends with Additives
149
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5.3.4 Task 3.4: The Selection of Final Additive 150
5.3.5 Summary of Stage 3 151
5.4 Economic Potential of Tailor-Made Green Diesel
Blends
5.5 Summary
151
153
6 PROPERTIES VALIDATION, ENGINE
PERFORMANCES & EMISSIONS
155
6.1 Introduction 155
6.2 Property Validation 155
6.3 Cetane Enhancement by 2-Ethyl Hexyl Nitrate 157
6.4 Engine Performances 158
6.4.1 Brake Thermal Efficiency (BTE) 160
6.4.2 Brake Specific Fuel Consumption (BSFC) 161
6.5 Emissions 162
6.5.1 NOx Emissions and Smoke Index 163
6.5.2 CO and UHC Emissions 166
6.6 Summary 169
7 CONCLUSION AND RECOMMENDATIONS 172
7.1 Conclusion 172
7.2 Recommendations 174
REFERENCES 176
Appendices A - E 197-221
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LIST OF TABLES
TABLE NO. TITLE PAGE
1.1 The main pollutants from diesel fuel 3
1.2 The flash point standard limits in various countries
(Thilagen and Gayathri, 2014)
9
2.1 Petrodiesel classification and its application (Song
et al., 2000, ASTM Standard, 2011)
14
2.2 The main components of the petrodiesel (Knothe,
2010, Song et al., 2000, Moser, 2012)
15
2.3 The evolution of European emission standards for
passenger cars (category M1) with diesel engine
(Ubrich and Jeuland, 2007)
16
2.4 The comparison of first, second and third
generation biofuels
18
2.5 Comparison of biodiesel, dimethyl ether, green
diesel and Fischer-Tropsch renewable diesel
26
2.6 The commercial biodiesel-petrodiesel blends 32
2.7 European and American standard for petrodiesel,
biodiesel and biodiesel/petrodiesel blends
38
2.8 The regulated fuel properties and the American
standard testing methods and limit values
40
2.9 Typical diesel fuel additives (GmbH, 2005) 46
2.10 Comparison of the methodology developed by
Ariffin Kashinath et al. (2012) and Hashim et al.
(2016) and Yunus et al. (2014)
50
2.11 Comparison of the mathematical regression flash
point prediction methods
53
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2.12 Comparison of vapor-pressure-based models 54
2.13 Comparison of different flash point models 60
2.14 Comparison of engine performance and emissions
of varied green diesel blends with petrodiesel
65
2.15 The principle causes of CO, NOx, PM and UHC
emissions
69
3.1 Summary of the methods/tools used in each
research tasks/sub-task
76
3.2 The green diesel requirements and the translated
target properties
80
3.3 The property constraints 81
3.4 Mathematical constraint models with target values
83
3.5 The requirements of green diesel blending agent,
translated target properties, and the target value
85
3.6 Fuel quality and property to enhance using
different additives
91
3.7 The composition of B5 adopted in this study which
is calculated from the composition of petrodiesel
(Fregolente et al., 2012) and POM (Mokhtarani et
al., 2009)
96
3.8 ATSM testing methods for each target fuel
properties
102
3.9 Specification of Yanmar L70N diesel engine 103
3.10 Steady state condition for engine performance and
emissions testing
106
4.1 Experimental flash point of B5-alcohol blends
111
4.2 Petrodiesel compositions used to study the effect of
variant petrodiesel composition towards the flash
point prediction
114
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4.3 The average obsolete deviation of the prediction
flash points obtained using the petrodiesel
compositions from (Fregolente et al., 2012)
compared to (Riser-Roberts, 1992) for petrodiesel-
POM and B5-EL, B5-ether and B5-alcohol blends
114
4.4 The list of denotation used to indicate how the
optimizations were done to revised UNIFAC group
interaction parameters
119
4.5 Revised group interaction parameters for Original
UNIFAC, NIST-UNIFAC, Modified UNIFAC
(Dortmund) and NIST-Modified UNIFAC model
120
4.6 AARDs obtained for test set data of B5-alcohol
blends using UNIFAC type models with the
revised parameter set B
126
4.7 Experimental flash point data of B5-EL-BU blends
together with its prediction accuracy (AARD)
129
5.1 The possible bio-resource to produce these selected
green diesel blending agents
136
5.2 Physicochemical properties of the main ingredient:
B5 and the blending agents used in this study
137
5.3 The results of the stability test of each B5
component with the selected bio-compounds
138
5.4 The immiscible ranges of the partial miscible
blends
140
5.5 The feasible region of each green diesel blends 141
5.6 The optimum green diesel blends ranked according
to the oxygen content
145
5.7 The possible cetane enhancers 149
5.8 The immiscibility gap of DTBP with B5
components
150
6.1 Comparison of the experimental and prediction
values for the fuel properties of GB3 and GT1
157
6.2 Comparison of the experimental fuel properties 157
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LIST OF FIGURES
FIGURE NO. TITLE PAGE
1.1 World CO2 emissions (IEA, 2015) 2
1.2 CO2 from different transportation (IEA, 2015) 2
1.3 Global biofuel production (BP, 2016) 4
2.1 The possible production routes of potential diesel
blending agents from biomass
29
2.2 The possible chemicals derived from furfural
(Lange et al., 2012b)
30
2.3 The possible chemicals derived from levulinic acid
(Yan et al., 2015)
30
2.4 Systematic computer-aided methodology of tailor-
made blended product Yunus et al. (Yunus et al.,
2014)
48
3.1 Tailor-made green diesel blend design algorithm 74
3.2 The common trend of Gibbs energy function of
mixing
86
3.3 Tangent plane condition 87
3.4 Generic work flow of Task 2.2 89
3.5 Overall work flow to validate and improve the
flash point prediction accuracy of Liaw model with
UNIFAC-type models for B5-ester/ether/alcohol
93
3.6 Algorithm for adjustment of group interaction
parameters using experimental flash point data
100
3.7 Blend preparation 102
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3.8 a) EMS emission analyzer; b) Bosch smoke meter 104
3.9 Schematic diagram of engine performance and
emission testing
104
3.10 Engine performance and emissions testing set up 105
3.11 a) script generated by smoke meter; b) Rubzahl-
Scale Comparative 177
108
4.1 Experimental and predicted flash point of diesel-
palm oil biodiesel blends. (♦) experimental flash
point (Mejía et al., 2013); (─ ─) Original UNIFAC
model; (----) Modified UNIFAC (Dortmund)
model; (──) Raoult‟s law (ideal curve)
113
4.2 Comparison of the experimental flash point of B5-
EL blend with the predicted flash point obtained
using Raoult‟s law (ideal curve), Original
UNIFAC, Modified-UNIFAC (Dortmund), NIST-
UNIFAC and NIST-Modified UNIFAC with
original group interaction parameters
115
4.3 Comparison of the experimental flash point of B5-
ether blends with the predicted flash point obtained
using Raoult‟s law (ideal curve), Original
UNIFAC, Modified-UNIFAC (Dortmund), NIST-
UNIFAC and NIST-Modified UNIFAC with
original group interaction parameters
116
4.4 Comparison of the experimental flash point of B5-
alcohol blends with the predicted flash point
obtained using Raoult‟s law (ideal curve), Original
UNIFAC, Modified-UNIFAC (Dortmund), NIST-
UNIFAC and NIST-Modified UNIFAC with
original group interaction parameters
117
4.5 Comparison of overall AARDs obtained using
original and revised parameter sets for training set
data of B5-alcohol blends. ( ) Original UNIFAC;
( ) NIST-UNIFAC; ( ) Modified UNIFAC
(Dortmund); ( ) NIST-Modified UNIFAC
124
4.6 Experimental and predicted flash point using
UNIFAC type models with original and revised
group interaction parameter set B for B5-alcohol
blends
127
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5.1 Generation of possible blending agent in ICAS-
ProCAMD.
135
5.2 Correlation between cost, the oxygen content and
the percentage of cetane number loss of the
shortlisted blends (see Table 5.8) compared with
B5
147
6.1 Comparison of fuel efficiencies of B5, GB3, GT1,
GB3A and GT1A
159
6.2 Emission of NOx and smoke 164
6.3 Emission of CO and UHC 167
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LIST OF ABBREVIATIONS
AAD - average absolute deviation
AARD - average absolute relative deviation
ASTM - American Society of Testing and Materials
BL - butyl levulinate
BMEP - brake mean effective pressure
BSFC - brake specific fuel consumption
BTE - brake thermal efficiency
BU - 1-butanol
BUDIOL - 1,4-butanediol
B5 - B5 palm oil biodiesel
CAMD - computer-aided molecular design
C=C - bonded alkyl chains
CCOO - esters group
CEN - European Committee for Standardization
CH2 - alkyl chains
CN - cetane number
CO - carbon monoxide
CO2 - carbon dioxide
DBE - dibutyl ether
DES - diethyl succinate
DGDE - diethylene glycol diethyl ether
DME - dimethyl ether
DPE - dipentyl ether
DTBP - di (tert-butyl) peroxide
EGR - exhaust gas recirculation
2EHN - 2-ethylhexyl nitrate
EL - ethyl levulinate
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EPA - Environmental Protection Agency
Eq. - equation
Exp. - experimental values
FAME - fatty acid methyl esters
F.B - free bound
FP - flash point
FT - Fischer-Tropsch
GAMS - Generalized Algebraic Modeling System
GHG - green house gases
HE - 1-hexanol
HHV - higher heating value
LLE - liquid-liquid equilibrium
LPG - Liquefied Petroleum Gas
M - miscible
MATLAB - Matrix Laboratory
MINLP - Mixed Integer Non-linear Programming
N2 - nitrogen
NO - nitrogen monoxide
NOx - nitrogen oxides
N2O - nitrous oxide
NO2 - nitrogen dioxide
N2O2 - di-nitrogen dioxide
N2O3 - di-nitrogen trioxide
N2O4 - di-nitrogen tetroxide
N2O5 - di-nitrogen pentoxide
NRTL - non- random two-liquid
OCT - 1-octanol
OH - alcohol group
P - partial miscible
PEN - 1-pentanol
PENDIOL - 1,5-pentanediol
PM - particulate matter
POM - palm oil biodiesel
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PV - pentyl valerate
ppm - part per million
Prep. - prediction values
QSPR - quantitative structure-property relationships
RSM - response surface methodology
rpm - revolution per minute (indicate engine speed)
SOx - sulfur oxides
SO2 - sulfur dioxides
SO3 - sulphur trioxide
Tb - boiling point
Tm - melting point
UHC - un-burnt hydrocarbon
ULSD - ultra-low sulfur diesel
UNIFAC - universal functional activity coefficient
UNIQUAC - universal quasichemical
VLE - vapor liquid equilibrium
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LIST OF SYMBOLS
𝐴, 𝐵, 𝐶 - parameter of Antoine equation
𝐴𝐴𝑅𝐷 - average absolute relative deviation
𝑎𝑚 ,𝑘 , 𝑏𝑚 ,𝑘 , 𝑐𝑚 ,𝑘 - group interaction parameter of UNIFAC type models
𝐵𝑆𝐹𝐶 - brake specific fuel consumption
𝐵𝑇𝐸 - brake thermal efficiency
Brake Power - brake Power
𝑐 - intercept of tangent plane
𝐶𝑁 - cetane number
𝑒𝑛𝑔𝑖𝑛𝑒 𝑠𝑝𝑒𝑒𝑑 - engine speed
Fobj - objective function
𝑓𝑢𝑒𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 - fuel consumption
∆𝐺𝑚𝑖𝑥 - Gibbs energy of mixing
𝐻𝐻𝑉 - higher heating value
𝐻2𝑂 - water content
heat input by fuel - heat input by fuel
m , k - main group for UNIFAC type models
max - maximize
min - minimize
𝑁 - total number of experimental data points
n - number of components
𝑂𝐶 - oxygen content
𝑃𝑠𝑎𝑡 - saturated vapor pressure
𝑃𝑖 ,𝐹𝑃𝑠𝑎𝑡 - vapor pressure of substance i at its flash point
𝑇 - temperature
𝑇𝐹𝑃 - flash point
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𝑇90 - distillation temperature at 90 volume % of distillate
recovered
𝑇95 - distillation temperature at 95 volume % of distillate
recovered
𝑇𝑜𝑟𝑞𝑢𝑒 - torque
𝑇𝑃𝐷 - tangent plane distance
𝑡 - slope of tangent plane
𝑥 - mass fraction
xFbio - the final maximum feasible composition of blending
agent
xLbio - maximum blending agent composition that match the
linear property constraints
xNLbio - maximum blending agent composition that match the
non linear property constraints
xPbio - maximum blending agent composition that is miscible
with B5
𝑥𝑚 - mole fraction
𝜂 - kinematic viscosity
𝜌 - density at 15 °C
𝜁 - target properties
𝛾 - activity coefficient
∑ - summation
⍱ - entire
> - greater than
>> - much more greater than
Subscripts
B5 - B5 palm oil biodiesel
BU - 1-butanol
bio - Biofuel/bio-chemical (blending agent)
com - components
D - petrodiesel
DBE - dibutyl ether
xxiv
DGDE - diethylene glycol
DPE - dipentyl ether
EL - ethyl levulinate
e - compound e
𝑒𝑥𝑝 - experimental value
𝐹𝑃 - flash point
f - compound f
GB - green diesel
HE - 1-hexanol
𝑖 - compound i
𝑚𝑖𝑥 - mixture
𝐿𝐿𝐸 - liquid-liquid equilibrium
PEN - 1-pentanol
POM - palm oil biodiesel
𝑝𝑟𝑒𝑑 - predicted value
𝑉𝐿𝐸 - vapor-liquid equilibrium
Superscript
𝛼, 𝛽 - two coexist phase at liquid-liquid equilibrium
xxv
LIST OF APPENDICES
APPENDIX TITLE PAGE
A Publication List 198
B UNIFAC Group Contribution Activity
Coefficient Model
200
C Vapor Pressure Prediction 202
D The Property Prediction Models for
Blending Agents
205
E The feasible Composition Ranges obtained
in Stage 2: Decomposition-Based Computer-
aided Optimization
210
CHAPTER 1
1 INTRODUCTION
1.1 Research Background
Fossil fuel remains the main energy resource for transportation (majorly
gasoline and petrodiesel) (IPCC, 2007); however, it is the largest source of the main
green house gases (GHG) emissions: carbon dioxide (CO2) after coal (IEA, 2015). In
year 2013, the transportation sector alone was responsible for around 23 % of world
CO2 emissions (see Figure 1.1) and road transport was the major CO2 contributor
compared to the other transportations (see Figure 1.2) (IEA, 2015). CO2 emission is
unlikely to reduce in the foreseeable future as the demand of the transportation fuel is
projected to grow up to nearly 40 % in year 2035, with the increasing population
(IEA, 2013).
Other than CO2 emissions, other emissions such as particulate matter (PM),
nitrogen oxides (NOx), carbon monoxide (CO), un-burnt hydrocarbon (UHC) and
sulfur oxide (SOx) have posed concerns. The main cause and the side-effects of these
emissions to environment and human are listed in Table 1.1. Diesel vehicle have
lower CO and UHC than petrol vehicle; however, diesel vehicle has much higher PM,
NOx and SOx when compared to petrol vehicle (Lee et al., 2011). These emissions
are carcinogens, especially for the respiratory suspended PM. Consequently, World
Health Organization recognizes these diesel vehicle emissions as carcinogen, and
these emissions are identified as the source of atmospheric haze (Geng et al., 2014).
2
*include fishing, energy industries other than heat generation and electricity, forestry or agriculture
and other not specified emissions
Figure 1.1: World CO2 emissions (IEA, 2015)
Figure 1.2: CO2 from different transportation (IEA, 2015)
3
Table 1.1: The main pollutants from diesel fuel
Pollutant Formation Side-Effect
Particulate matter, PM result of incomplete
combustion (Kim et al.,
2002)
severe effect to
environment and human
health as it could lead to
asthma, lung cancer and
increased blood pressure
(Geng et al., 2014)
Nitrogen oxide, NOx formed when diesel
combusts in high
temperature (Sayin, 2010)
leads to respiratory
problem and it causes the
formation of PM, acid
rain, smog and ground
level ozone, which are
adversely affecting human
health (Icopal, 2016)
Carbon monoxide, CO is a product of incomplete
burning of fuel due to
insufficient air supply
(Sayin, 2010)
has the potential to form
ground level ozone and
can cause neurological
damage and harm to
unborn baby if expose to
low CO concentration for
a long term (SEPA, 2016)
Un-burnt hydrocarbon,
UHC
formed when the un-
burned or partially burned
fuel is released from diesel
engine
toxic and carcinogenic; it
can react with NOx under
sunlight to form ozone
(MED, 2016)
Sulphur oxide, SOx generated because of the
combustion of the sulfur-
containing compounds,
which is naturally present
in petrodiesel fuel.
is the precursor of acid
rain and it affects
respiratory system
(Queensland Government,
2016)
In order to mitigate these carcinogenic diesel emissions (see Table 1.1), a
greener alternative energy resource is essential. Biofuel is one of the promising
solutions to address this emission issue. Biofuel is renewable; it can be derived from
any biomass including vegetable oil, agriculture waste (e.g. rice straw and empty
fruit branch) and any lignocellulosic resources. Using biofuel to run diesel vehicle
prompts to CO2 equivalence as the CO2 generated by a running diesel vehicle can be
offset by plant for photosynthesis (Tan et al., 2011). On the other hand, nearly zero
sulfur containing compounds are present in biofuel; hence, the issue regarding SOx
emissions is mitigated (Yaakob et al., 2013). The oxygen bonded biofuel provides
lean-combustion by its self-provided oxygen; therefore, it can potentially reduce the
emissions of PM (Zhang et al., 2016), CO (Li et al., 2014) and UHC (Atmanli et al.,
4
2015). In addition, most biofuel could lower the combustion temperature and NOx
emission can be reduced (Chang et al., 2013).
The world of biofuel production has grown positively since 2005 as
illustrated in Figure 1.3. Biodiesel is the main biomass renewable fuel produce for
petrodiesel replacement as compared to other biofuel such as alcohol. Biodiesel is
majorly produced by transesterification of vegetable oil with alcohol, mainly
methanol (Aransiola et al., 2014). The world biodiesel production is still mainly
relying to the edible oil and this biodiesel is recognized as the first generation biofuel
as it is from edible resources (Larson, 2008, Demirbas, 2009). Malaysia is one of the
representatives from the Asian countries to produce biodiesel using palm oil.
Nowadays, the second generation biofuel, which is produced from non-edible
resources and waste biomass (lignocellulosic material), has become more important.
Thermochemical (pyrolysis, gasification) and biochemical (fermentation) processes
are the common production routines to convert the lignocellulosic material into
valuable biofuel (Schlichter and Montes, 2011), for example alcohols (e.g.
bioethanol, biomethanol, biobutanol and linear bioalcohol mixed), Fischer-
Tropsch renewable diesel (a mixture of carbon chains), ethyl levulinate (Huber et
al., 2006), dimethyl ether (Chen et al., 2012) etc.
(a) global biofuel production by region in
million tonnes oil equivalent
(b) global biofuel production by types in
million tonnes oil equivalent
Figure 1.3: Global biofuel production (BP, 2016)
Year
5
Biofuel could efficiently reduce harmful emissions, but being able to fully
replace petrodiesel with biofuel is undesired. Biodiesel have higher viscosity than
petrodiesel fuel; it will cause engine filters clogging and engine modification is
needed to run diesel engine with biodiesel (Sorate and Bhale, 2015). Dimethyl ether
has totally different physical properties with petrodiesel hence the storage and fuel
transport and injection system are needed to alter (Kim et al., 2011, Semelsberger et
al., 2006). Furthermore, green diesel (Kordulis et al., 2016) and Fischer-Tropsch
renewable diesel (Im-orb et al., 2016) have similar physicochemical properties with
diesel; however, new refinery plant is required for large scale production. These vast
technology evolutions lead to unaffordable implementation cost and immediately
stopping the petrodiesel supply that is not economically feasible. Hence, blending
petrodiesel with biofuel or bio-chemical becomes beneficial.
Tailor-made green diesel blend, which is interpreted as the blend of
petrodiesel with oxygenated biofuel/bio-chemical (bio-ester, bio-ether and bio-
alcohol), is superior to reduce harmful emission while retaining or even improving
the engine performance with acceptable implementation cost. Biofuel/bio-chemical
acts as the oxygenate „additive‟ to petrodiesel to enhance complete fuel combustion;
hence, reduces the most carcinogenic emissions like PM, UHC and CO in the
exhaustion stream. For instance, biodiesel-petrodiesel blend is a commercial tailor-
made green diesel blend. This blend has been commercialized in European Union,
United States and Asian countries including Malaysia. Biodiesel-petrodiesel blend
does not only reduce harmful diesel emissions; it prolongs engine life by improving
the lubricity of petrodiesel fuel (Knothe and Steidley, 2005). Unfortunately,
biodiesel-petrodiesel blends generally have higher NOx than petrodiesel (Can et al.,
2016). Furthermore, enhancing the combustion and fuel properties of this green
diesel blend to attain greener and more efficient fuel is important.
Nowadays, green diesel blends containing lignocellulosic biofuel/bio-
chemicals, such as bio-ester, bio-ether and bio-alcohol are getting more attention due
to their excellent fuel properties (Koivisto et al., 2015), (Chauhan et al., 2016) and
(Campos-Fernández et al., 2012a). In addition, utilization of lignocellulosic
biofuel/bio-chemical mitigates the conflict between food and fuel as the current
6
biodiesel production is mainly relying on edible vegetable oil. Blending oxygenated
biofuel/bio-chemicals with petrodiesel can significantly reduce harmful emissions;
however, it might deteriorate the fuel combustion quality by reducing both cetane
number (CN) and higher heating value (HHV) of petrodiesel. This happened because
biofuel/bio-chemical generally has lower HHV and CN than petrodiesel. Using diesel
fuel with lower HHV and CN will leads to higher fuel consumption (Pandey et al.,
2012) and engine knocking (Lim et al., 2012). In order to reduce the harmful
emissions without significantly drop the fuel quality, the main concerns always
related to tailor-made green diesel blend design problem are on how to define the
blend target properties and how to find blends that match these targets. This design
problem can become more complex and complicated with the infinite number of
possible blending agents as it results to limitless possibility of blending candidate.
A systematic computer aided approach can efficiently solve this tailor-made
green diesel blends design problem by providing a more efficient solution method
than the iterative trial and error approach (Gani, 2004). This method had been widely
applied to design skin-care cream (Cheng et al., 2009), paint and insect repellent
(Conte et al., 2011), gasoline blends and lubricant base oils (Yunus et al., 2014) etc.
The computer aided technique is able to rapidly narrow down the search space of
feasible green diesel blends so that the costly and time consuming experimental
works can be done only on the selected promising candidates. This research is
carried out to obtain an optimum tailor-made green diesel blends containing B5 palm
oil biodiesel by using a decomposition-based computer-aided approach and
subsequently, to validate the property and performance of the designed fuel blend
using experimental works.
1.2 Problem Statement
Malaysia has launched the National Biofuel Policy in year 2006 to
commercialize palm oil biodiesel and to promote the use, export and research on
biodiesel and other renewable fuel from biomass, mainly focusing on lignocellulosic
7
biomass (Chin, 2011). B5 palm oil biodiesel (B5) mandate was launched in
Malaysia since 2011 by region (started from the central regions: Kuala Lumpur,
Selangor, Putrajaya and Melaka) and it was fully implemented nationwide on July,
2014. Meanwhile, Malaysia prospected to achieve Euro 5 emission standard diesel
fuel in year 2020 in order to cut off 40 % carbon footprint in year 2020 compared to
year 2005 (Begum and Pereira, 2011). Unfortunately, the use of biodiesel always
leads to higher NOx emissions and this increment will become significant when more
biodiesel is blended with petrodiesel (Man et al., 2016). Furthermore, highly relying
on edible palm oil-based biodiesel can induce the conflict between food and fuel and
raising the food (palm oil) price. In order to get an alternative diesel fuel blend with
greener emissions and higher portion of biofuel/bio-chemical, it is essential that
other lignocellulosic bio-chemicals with excellent fuel and combustion
characteristics (e.g. high oxygen content and cetane number) to be introduced into
B5.
The main concern related to the tailor-made green diesel blend design
problem is how to find the suitable blending agent (biofuel/bio-chemicals) and how
to find the blends with desired target properties. Trial and error is a traditional
experimental method used to solve a blending design problem. This method is
unfavorable as numerous repeats and varied attempts are needed and continued until
the problem is successfully solved. It will become more troublesome and expensive
when a blending design problem has enormous possible blend candidates. Hence, a
systematic computer aided tailor-made green diesel blend design algorithm is
essential to solve the blending design problem. Ariffin Kashinath et al. (2012)
computationally design petrodiesel-ethanol, butanol and/or butyl levulinate blends
based on linear property models of density, viscosity, distillation temperature and
cetane number without performing experimental validation. Hence, the accuracy of
the design method presented by Ariffin Kashinath et al. (2012) is unknown. Hashim
et al. (2016) extend the works presented by Ariffin Kashinath et al. (2012) by
introducing experimental validation. A more comprehensive computer-aided blended
product design algorithm is introduced by Yunus et al. (2014). This method was used
to design gasoline and lubricant blends from molecular level up to the end product;
but, no experimental validation is performed and this generic method is not used to
8
design green diesel blends. None of the foregoing methods consider fuel additive (e.g.
cetane enhancer) to enhance the design blends in their design algorithm whereas it
could be very important as some of the fuel properties are difficult to attain by solely
using blending agent/s (bio-chemical/s). In addition, another important safety related
fuel properties: flash point is not involved in the foregoing studies in the computer-
aided design stage.
Flash point of a liquid petroleum product is defined as the lowest temperature
at which the fuel must be heated to produce sufficient vapors that ignite
spontaneously in the present of a flame (Crowl and Louvar, 2002). Flash point is
rarely been considered in the early green diesel blend design stage as it has no
directly effects on engine performance and combustion. However, it is a very
important information related to handling safety, such as distribution operation and
storage condition (Dharma et al., 2016). On the contrary to the lighter petrol fuel, in
which its flash point is much lower than 0 ˚C (- 43˚C) and it is always too rich to
ignite under atmosphere when contact to a flame as its vapor concentration in air is
above the upper flammable limit of gasoline, the flash point of the heavier diesel fuel
must be high enough to prevent fire accident. Table 1.2 showed the flash point
standard values of diesel in few countries. Overall, the flash point values are above
50 ˚C, except in India. As reported by (Thilagen and Gayathri, 2014), numerous fire
accidents occurred in India due to the low flash point of diesel fuel as it can easily
cause explosion of diesel tank when transport vehicles collided. On the other hand,
Guibet and Faure-Birchem (1999) comments that blending gasoline to petrodiesel
fuel should be prohibited as unacceptable flash point reduction happened and causing
gasoline-petrodiesel blend to be highly flammable under atmosphere. Hence, it is
important to have diesel fuel with high flash point and it should not be omitted when
designing green diesel blends.
9
Table 1.2: The flash point standard limits in various countries (Thilagen and
Gayathri, 2014)
Country Diesel flash point, ˚C
China 66
Pakistan 66
Australia 61
Malaysia 60
Norway 60
Srilanka 60
Germany 56
U.K 56
Finland 55
Italy 55
Netherlands 55
U.S.A 54
Thailand 52
Ireland 51
Japan 50
India 35
An accurate flash point prediction model is needed to design green diesel
blends containing B5 with safe handling characteristics. Liaw model (Liaw et al.,
2002) is a reliable flash point prediction model to predict the flash point of non-ideal
mixture. It has been widely applied to predict the flash point of binary (Liaw et al.,
2002) or binary aqueous (Liaw and Chiu, 2003) mixtures; ternary (Liaw et al., 2004)
or ternary aqueous (Liaw and Chiu, 2006) mixtures; biodiesel-ethanol blends (Guo et
al., 2009a, Khalili and Zarringhalam Moghaddam, 2011); and varied partially
miscible mixtures (Liaw et al., 2008a, Liaw et al., 2008b, Liaw et al., 2009, Liaw et
al., 2010). The accuracy of Liaw model is highly dependent to the activity coefficient.
As the molecular binary interaction parameters that are needed for e.g. Wilson,
NRTL and UNIQUAC activity coefficient models are always not available for many
compounds; UNIFAC-based model is preferred. Only group-group interaction
parameters, which are widely available and updated from time to time, are needed to
calculate the activity coefficient using UNIFAC-based model. Hence, UNIFAC-
based Liaw model shows great potential to predict the flash point for varied tailor-
made green diesel blends that contain B5. Unfortunately, the accuracy of the
UNIFAC-based Liaw model haven‟t been validated for green diesel blends
containing B5 and its accuracy is needed to verify in order to have a reliable green
diesel blends design algorithm.
10
In conclusion, there is a need to develop a comprehensive systematic
computer-aided tailor-made green diesel blend design algorithm to obtain green
diesel blends that match the desired target fuel properties and with lower emissions
than B5. The design algorithm must able to computationally design the optimum
green diesel blend by finding the suitable blending agent to blend with B5 in order to
look at every single potential binary and ternary blend candidates (by pairing each
generated blending agent with B5); and considering fuel additives to further enhance
the design blends. Experimental validation must be performed at the end of the
design algorithm to study the optimum blends experimentally for further
development. In addition, the prediction accuracy of the flash point prediction model:
UNIFAC-based Liaw model for the green diesel blend containing B5 need to be
checked and improved when needed.
1.3 Research Objectives
The aim of this research is to propose an integrated systematic computer-
aided framework with experimental approach to obtain tailor-made green diesel. To
achieve this goal, the sub-objectives are listed as follows:
1. To develop a systematic computer-aided tailor-made green diesel blend
design algorithm for tailor-made green diesel blend design problem.
2. To improve flash point prediction model based on the Liaw model for green
diesel fuel blend.
3. To validate the physicochemical properties and determine engine
performances and emissions of the designed optimum green diesel blends
using experimental works.
11
1.4 Research Scopes
In order to attain the aforementioned objectives, the research scopes have to
include the followings:
1. Retrieve the required data (e.g. fuel properties) from the database of the
computer tool: ICAS version 17.0 or literature, if available.
2. Generate the possible blends candidates (with ester, ether and alcohol) using
computer-aided molecular design tools: ICAS-ProCAMD.
3. Optimize the tailor-made green diesel blends containing B5 with
ester/ether/alcohol using simulator-optimizer/calculation of MATLAB software.
4. Verify and improve the flash point prediction accuracy of the Liaw model using
UNIFAC type models for B5-ester/ether/alcohol blend, and embed the
improved flash point prediction model to optimize the green diesel blends.
5. Perform experimental works to validate the fuel properties and measure the
engine performances and emissions of the design diesel blends in a four-stroke
diesel engine.
1.5 Research Contribution
The main contribution of this research is an improved model-based method
for tailor-made green diesel blends design as compared to the traditional trial and
error experimental approach. The specific research contributions are listed as follows:
1. Contribution 1: A new systematic tailor-made green diesel blends design
algorithm for tailor-made green diesel blend design.
2. Contribution 2: Improved flash point prediction model for tailor-made
green diesel blends contains B5.
3. Contribution 3: New tailor-made green diesel blends, which are safer for
environment and humans with less pollutants and green house gasses
release as compared to the conventional B5, are obtained.
12
A substantial part of the results obtained in this research is published in international
journals and presented in international conferences. The list of research publications
and attended conferences can be found in Appendix A.
1.6 Thesis Outline
This thesis is divided into seven chapters. Chapter 1 introduces the research
background, problem statement, research objectives, scopes and contributions of the
presented study. A comprehensive literature review is provided in Chapter 2. Chapter
3 describes the research methodology that comprises of the systematic computer
aided tailor-made green diesel blend design algorithm, improvement of flash point
prediction accuracy for tailor-made green diesel blends containing B5 and
experimental validation and measure of the physicochemical properties and engine
performances and emissions of the optimum green diesel blends. Chapter 4 describes
the results obtained for flash point model improvement while the results obtained for
green diesel blend optimization using the developed design algorithm is presented in
Chapter 5. Subsequently, the experimental results of the physicochemical properties
and engine performances and emissions of the optimum green diesel blends are
discussed in Chapter 6. Finally, Chapter 7 summarizes the main findings obtained in
this research.
176
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